CN1839045A - Liquid drop placing device and liquid drop placing method - Google Patents
Liquid drop placing device and liquid drop placing method Download PDFInfo
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- CN1839045A CN1839045A CNA2005800007599A CN200580000759A CN1839045A CN 1839045 A CN1839045 A CN 1839045A CN A2005800007599 A CNA2005800007599 A CN A2005800007599A CN 200580000759 A CN200580000759 A CN 200580000759A CN 1839045 A CN1839045 A CN 1839045A
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- ink gun
- substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/015—Ink jet characterised by the jet generation process
- B41J2/04—Ink jet characterised by the jet generation process generating single droplets or particles on demand
- B41J2/045—Ink jet characterised by the jet generation process generating single droplets or particles on demand by pressure, e.g. electromechanical transducers
- B41J2/04501—Control methods or devices therefor, e.g. driver circuits, control circuits
- B41J2/04586—Control methods or devices therefor, e.g. driver circuits, control circuits controlling heads of a type not covered by groups B41J2/04575 - B41J2/04585, or of an undefined type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/015—Ink jet characterised by the jet generation process
- B41J2/04—Ink jet characterised by the jet generation process generating single droplets or particles on demand
- B41J2/045—Ink jet characterised by the jet generation process generating single droplets or particles on demand by pressure, e.g. electromechanical transducers
- B41J2/04501—Control methods or devices therefor, e.g. driver circuits, control circuits
- B41J2/04556—Control methods or devices therefor, e.g. driver circuits, control circuits detecting distance to paper
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- Coating Apparatus (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Ink Jet (AREA)
Abstract
A liquid drop placing device includes an inkjet head (1), a substrate (13) receiving a liquid drop (2) discharged from the inkjet head (1), a device for irradiating or reflecting light from a nozzle hole or its vicinity of the inkjet head (1) toward the substrate (13), a position moving device (10) for controlling relative positions between the inkjet head (1) and the substrate (13), and a control device (9) for discharging liquid from the inkjet head (1). Behind the substrate (13), when seen from the inkjet head (1), is provided a photo receiving element (6) for recognizing the position of the inkjet head (1). The substrate (13) has transparency of the extent where the light irradiated or reflected at least from the nozzle hole or its vicinity toward the substrate (13) enters in the photo receiving element (6), and the photo receiving element (6) detects the light irradiated or reflected from the nozzle hole or its vicinity toward the substrate (13). As a result, relative positions of the inkjet head and the substrate are accurately adjusted even if the distance between the two is short.
Description
Technical field
The present invention relates to use the droplet configuration device and the droplet configuration method of ink-jet.
Background technology
In recent years, ink-jet printer on the other hand, also is utilized the manufacturing installation of making electronic installation and DNA (DNA) chip as the printing machine of literal and image and be widely used.Here, so-called electronic installation is meant the element or its aggregate that utilize the mobile and savings of electronics, the savings that carries out computing, information and transmission, demonstration etc.As their example, electric circuit is arranged, constitute their wiring, electrode, resistive element, capacitor, semiconductor element etc.
The summary of ink-jet printer and the electronic installation Production Example of being undertaken by ink-jet printer below are described.The structure of the printing of ink-jet printer, the a plurality of through holes (below be called " nozzle bore ") that are the diameter tens μ m that offer from dull and stereotyped (below be called " nozzle plate ") are respectively to lettering bodies such as the paper China ink that several skins rise that spues, and the China ink that spues are configured on the position of regulation of lettering body.On the position for the regulation that China ink is configured in recording medium, mechanically change the position of nozzle plate and lettering body, Yi Bian control their relative position, Yi Bian the China ink that spues.Like this, the method that liquid (being also referred to as drop) is configured on the assigned position of base material that will spue from the nozzle bore of nozzle plate is called ink-jet method.In addition, will have from the spue device of mechanism of liquid of nozzle bore and be called ink gun.Ink gun has nozzle plate, connects the nozzle bore of nozzle plate, with nozzle plate spue with liquid that the opposite face of face contacts and lead to the balancing gate pit of nozzle bore and the mechanism of generation pressure in the balancing gate pit.Then, by the balancing gate pit is exerted pressure, the liquid that remains in the balancing gate pit is spued outside nozzle plate from nozzle bore.
Figure 10 is the skeleton diagram of ink-jet printer integral body.The ink gun 101 that the piezoelectric effect of utilizing piezoelectric element of having the ink-jet printer 100 of Figure 10 writes down makes the ink droplet that spues from this ink gun hit at recording mediums such as paper 102 to come recording medium is carried out record.Ink gun carries on the balladeur train 104 that is disposed on the main scanning direction X, moves back and forth and moves back and forth on main scanning direction X along balladeur train axle 103 corresponding to balladeur train 104.And then, ink-jet printer have make recording medium with the sub scanning direction Y of width (directions X) vertical direction of ink gun 101 on a plurality of rollers (travel mechanism) 105 of relatively moving.Ink-jet printer by the nozzle plate of nozzle bore with the China ink that spues, make drive part that China ink spues from nozzle and the part that China ink supplies to nozzle constituted.
Figure 11 A-C represents an example of the structure of ink gun.Figure 11 A is nozzle bore 121 and near cutaway view thereof.Nozzle bore leads to balancing gate pit 113, and 113 top is formed with oscillating plate 112 and piezoelectric element 111 in the balancing gate pit.Be full of inking in balancing gate pit 113, China ink is supplied with by black supply hole 114 from black stream 115.If piezoelectric element 111 is applied voltage, then piezoelectric element 111 and oscillating plate 112 bendings, the pressure of balancing gate pit 113 rise and from nozzle 121 China ink that spues.Hydrophobic treatment has been implemented on nozzle plate 116 surfaces, so that China ink 118 spues to certain direction from nozzle bore 121.In order to improve the pressure of balancing gate pit 113, the situation (bubble jet (Bubble Jet) (registration mark) method) of the method that makes black indoor generation bubble is arranged also.Figure 11 B is with the signal perspective view after the I-I line cut-out of Figure 11 A.Here only represent near the structure about 2 nozzle bores, but the forming a line of in fact a plurality of and its same configuration.Among the figure, the piezoelectric element 117 of having represented the left side and oscillating plate 112 bendings, from nozzle bore 121 to the spue situation of China ink 118 of the direction of arrow 119.In addition, as seen from the figure, having distributed 1 balancing gate pit 113 and piezoelectric element 117 for each nozzle bore, is general but supply with black black stream 115 for a plurality of nozzle bores, and China ink is supplied with by the black supply lines 114 that is opened in each balancing gate pit 113 from stream.Figure 11 C is the vertical view of observing from nozzle plate top.In this example, it is wide to be spaced apart about 340 μ m, about one list the nozzle bore 121 of having arranged 40 up and down 2 row arranged.Among the figure, the line 120 that surrounds each nozzle is the shapes that are positioned to the piezoelectric element of nozzle plate one side, the shape of the black stream of dotted line 124 expressions.Because 40 nozzle bores arranging to the left and right from a black stream are supplied with China ink, thus from about the spue China ink of same color of 40 nozzle bores.122 the expression base materials direction of feed, 123 the expression nozzle arrangement 2 row states.
Below the typical example of electronic installation manufacturing installation is done the ink-jet printer utilization in expression.Have by metallic colloid being depicted on the printed base plate, having formed the example (following Non-Patent Document 1) of the line pattern of lead on printed base plate by ink-jet method.Usually, in order on printed base plate, to form conductive circuit pattern, use in advance and after forming metal film on the substrate, form the wire circuit figure or in the zone that after formation, does not have resist behind the negative patterning that forms circuit on the substrate with the plating method, form the wire circuit figure, the method for removing resist then with resist film by photoetching process.Using the advantage of ink-jet method is directly to form circuit on printed base plate without the photo-mask process of taking time and energy.Therefore, circuit forms and becomes the short time, can significantly reduce manufacturing cost.And then, because need be in photoetching process, so under the situation of the trial production of the production of the circuit that carries out a small amount of many kinds or various circuit, need to make a large amount of photomasks, time and cost increase corresponding to the photomask (version) of manufacturing circuit.Relative therewith, owing in ink-jet method, do not need photomask, so be suitable for the circuit production of a small amount of many kinds, the trial production of circuit.
In addition, have by on substrate, describe functional organic molecule by ink-jet method form field-effect transistor (following Non-Patent Document 2), utilize electroluminescent display (following Non-Patent Document 3), the example of micro lens array (following Non-Patent Document 4) etc.Have if the functional organic molecular film that forms on substrate is exposed in the developer solution of resist or the stripper from base material and peel off or the trend of electric property deterioration, be difficult to form figure by common photo-mask process.Ink-jet method be owing to can make the deterioration in characteristics of functional organic molecule and form figure simply, so be promising as the manufacture method of the electronic installation that uses organic molecule.
In addition, in recent years, the DNA chip is widely used as being used for the mechanism according to genic horizontal detection people's physique, the diagnosis of disease, the effectiveness mode of medicine etc.So-called DNA chip, be thousands of～tens thousand of kinds of dna fragmentations or synthetic oligonucleotide (following they are called " dna probe ") to be separately fixed on the assigned position of the glass substrate on several centimetres four limits or silicon substrate etc. form, with the situation of measuring many genic discoveries simultaneously or detect whether there is specific gene be that purpose is used.Proposed to make the method for this DNA chip with ink-jet method.That is, be configured to ink-jet method by the liquid that will dissolve dna probe on the position of regulation of base material, can form DNA chip (following Patent Document 1) with low cost easily.
In order to make electronic installation and DNA chip, need correctly liquid to be configured on the assigned position of substrate with ink-jet method.Generally, preestablish the initial position of ink gun and substrate, while, liquid is configured on the assigned position of substrate by making the head and the relative position of substrate be offset the amount that the is predetermined drop that spues.If the figure of the drop of describing is about hundreds of μ m, then can enough this methods correctly describe.But, since the influence of the thermal expansion of the initial position of ink gun and substrate or the fixed form that amount of movement is subjected to substrate, base material that variations in temperature is brought and in the scope of μ m sheet example (dispersing), so the figure of describing μ m～tens μ m with said method is very difficult.
In addition, in the liquid that uses ink gun spues, though rare, there is nozzle bore to stop up and situation that liquid can not spue.For repeatability is made electronic installation and DNA chip well, whether the detection drop spues exactly also is very important.
In following Patent Document 2, proposed to make reactive material to be fixed on spotting device on the ad-hoc location of test section.In this special permission, the position of the vision camera identification substrate of the oblique upper of the substrate by being arranged on the configuration drop correctly is configured in drop on the substrate.
In addition, in following Patent Document 3, proposed to possess the ink gun of a plurality of nozzles and above-mentioned hair is gone out from the spue dna probe solution device for discharging fixed of mechanism of driving signal of liquid of the nozzle of regulation, it is characterized in that having to the light projector mechanism of the solution light projector that spues from said nozzle and be subjected to the optical mechanism that is subjected to of light from above-mentioned light projector mechanism with the dna probe solution that spues.Whether the direction of light that penetrates is parallel with the face that spues of ink gun, by accepting the light by the reflection liquid that from the beginning spues, detect solution and normally spue.
In addition, in following Patent Document 4, the manufacture method of the organic el display of following formation has been proposed: when forming organic layer on the pixel on substrate spue the liquid phase organic material by ink-jet method, (a) on substrate, form the image recognition figure in advance, (b) obtain substrate or locations of pixels information by discern above-mentioned image recognition figure by pattern recognition device, (c) according to aforesaid substrate or locations of pixels information, the moment of control ink gun and substrate or the locations of pixels cooperation and the liquid phase organic material that spues.In the document, show pattern recognition device is discerned figure in the rear side of substrate, by transparent or semitransparent substrate recognition image with respect to the ink gun fixed configurations method.At this in the past in the example, not open for the illumination light that the recognition image recognition device is required with respect to the allocation position of substrate or image.
According to present inventors' result of study up to the present as can be known, in order to be configured in the fine liquid drops figure below the hundreds of μ m, need make being spaced apart below the 1mm of discharge opening and substrate.This is because if should be at interval bigger, then the liquid that comes out from discharge opening changes the direction of circling in the air attached to being subjected to cross-ventilated influence during on the substrate.And then, if bigger at interval, the situation that also has small drop before being attached on the substrate, to vapor away.
In the device shown in the Patent Document 2, because vision camera is configured in the substrate oblique upper, so if being spaced apart below the 1mm of discharge opening and base material then be can't see the position of the substrate under the discharge opening.Particularly, under the situation with the ink gun of arranged in high density discharge opening on the nozzle plate, be in substrate location under near the nozzle bore the nozzle plate center and be the behind of nozzle plate end and can not detect by vision camera.
Equally, in the device shown in the Patent Document 3, owing to need the parallel light of enemy (head) irradiation, so if the interval of head and substrate shortens, then light is difficult to incide between them.
In Patent Document 4, because the corresponding ink gun of vision camera is configured in the dorsal part of substrate, so, also can observe the zone of the substrate that will dispose drop even the interval of ink gun and substrate diminishes.And for the position with vision camera identification ink gun or substrate, need utilize light source that light is radiated on ink gun or the substrate, makes from the light of its reflection and incide the vision camera, but in Patent Document 4, for how to carry out configured light sources not openly.Generally, use light source is placed method between vision camera and the substrate.But, in the method, in order to dispose light source the distance of substrate and vision camera is left, under the zone of the substrate that will discern is situation about μ m, in order enough vision camera to catch this small zone, need large-scale optical system, become big so device is whole.Therefore, the position of vision camera has to fix.Vision camera also is fixed in Patent Document 3.Under only some mobile situations of substrate or ink gun, the relative position relation of substrate and ink gun can utilize arithmetic processing circuit to derive simply based on the information that obtains from vision camera.On the other hand,, need to improve the speed of droplet configuration, so on one side must be on one side make ink gun and substrate mobile simultaneously from a plurality of nozzle bores drop that spues simultaneously for ink-jet method volume production electronic installation.In this case, since each moment of the relative position relation of vision camera and substrate and vision camera and a plurality of nozzle bores all in conversion, so in order to derive the relative position relation of substrate and ink gun, arithmetic processing circuit becomes on a large scale.These results that bring are the problem that the price that the droplet configuration device of Patent Document 4 has optical system and arithmetic processing circuit to become on a large scale, install also uprises.
Patent Document 1: United States Patent (USP) 5,658, No. 802 specifications
Patent Document 2: TOHKEMY 2003-98172 communique
Patent Document 3: TOHKEMY 2002-253200 communique
Patent Document 4: TOHKEMY 2001-284047 communique
Non-Patent Document 1:G.G.Rozenberg, Applied Physics Letter, 81 volumes,, P5249-5251 in 2002
Non-Patent Document 2:H.Sirringhaus etc., Science,, 290 volumes, P2123-2126 in 2000
Non-Patent Document 3:J.Bharathan etc., Applied Physics Letter, 72 volumes,, P2660-2662 in 1998
Non-Patent Document 4:T.R.Hebner etc., Applied Physics Letter, 72 volumes,, P519-521 in 1998
Summary of the invention
Lack the relative position that also can correctly adjust ink gun and base material, the droplet configuration device that can also observe the state that spues of drop even the invention provides the distance of a kind of ink gun and substrate.Also provide and be used for drop correctly is configured in method on the substrate.
Droplet configuration device of the present invention has: ink gun; Substrate is accepted the drop that spues from above-mentioned ink gun; Shine or catoptrical device to aforesaid substrate from nozzle bore or its periphery of above-mentioned ink gun; Location mobile device is controlled the relative position of above-mentioned ink gun and aforesaid substrate; Control device will spue from the liquid of above-mentioned ink gun; Wherein, the photo detector of discerning the position of above-mentioned ink gun is configured in from the rear of the aforesaid substrate of above-mentioned ink gun observation; Aforesaid substrate has to be made from the said nozzle hole or the transparency of the degree that its periphery enters into photo detector to the irradiates light or the reverberation of aforesaid substrate; Above-mentioned photo detector detect from the said nozzle hole or its periphery to the irradiates light or the reverberation of aforesaid substrate.
Droplet configuration method of the present invention, be to spue liquid and aforesaid liquid is configured in the lip-deep method of aforesaid substrate from ink gun, it is characterized in that, photo detector is configured in the liquid exhaust end of above-mentioned ink gun, again aforesaid substrate is configured between above-mentioned ink gun and the above-mentioned photo detector, before the aforesaid liquid that spues, measure the position of above-mentioned ink gun by above-mentioned photo detector, determine the relative position of above-mentioned ink gun and aforesaid substrate aforesaid liquid to be configured on the aforesaid substrate according to above-mentioned measured information.
Description of drawings
Fig. 1 is the droplet configuration schematic representation of apparatus of expression embodiments of the present invention 1.
Fig. 2 is the schematic diagram of the relation of the substrate of droplet configuration device of expression embodiments of the present invention 1 and photo detector.
Fig. 3 A is the droplet configuration schematic representation of apparatus of expression embodiments of the present invention 2, and Fig. 3 B is the upward view of the ink gun of Fig. 3 A.
Fig. 4 is the droplet configuration schematic representation of apparatus of expression embodiments of the present invention 3.
Fig. 5 is the droplet configuration schematic representation of apparatus of expression embodiments of the present invention 3.
Fig. 6 is the generalized section of the ink gun of expression embodiments of the present invention 3.
The schematic diagram of the situation that Fig. 7 light that to be expression emit from the nozzle bore of the ink gun of embodiments of the present invention 3 is accepted by optical sensor.
Fig. 8 is the droplet configuration schematic representation of apparatus of expression embodiments of the invention 1.
Fig. 9 is the schematic diagram of the details of the light reflector element of droplet configuration device of expression embodiments of the invention 1 and photo detector.
Figure 10 is a schematic diagram of representing the integral body of ink gun in the past.
Figure 11 A～Figure 11 C is the schematic diagram of the ink gun representing in the past to use, also use in embodiments of the invention 1, Figure 11 A is near the profile schema diagram of the ink gun the nozzle bore, Figure 11 B is the signal perspective view by the I-I line cut-out of Figure 11 A, and Figure 11 C is the schematic diagram from the ink gun of nozzle plate side observation.
The specific embodiment
Droplet configuration device of the present invention has the photo detector of the position of the rear that is present in the aforesaid substrate when above-mentioned ink gun is observed, the above-mentioned ink gun of identification.In addition, aforesaid substrate has the transparency that makes the degree that enters into photo detector to the irradiates light or the reverberation of aforesaid substrate from the nozzle bore of above-mentioned ink gun or its periphery at least.Though transparency is high more preferred more, and is translucent also no problem.So long as photo detector can detect from the said nozzle hole or its periphery is just passable to the transparency of the irradiates light of aforesaid substrate or catoptrical degree.As substrate, preferably use transparent resins such as glass substrate or polyester substrate, allyl resin substrate, polyene substrate.
Substrate also can be fixed on the fixed station of other setting.Be preferably, above-mentioned photo detector also moves integratedly with the said fixing platform when the said fixing platform moves.
In addition, in this droplet configuration device, be preferably, between said fixing platform and above-mentioned photo detector, be provided with the translucent reflecting plate of light, the configuration light source is so that the light parallel with the face of aforesaid substrate incides on the said reflection plate, adjust the configuration of said reflection plate, be transmitted to above-mentioned photo detector side so that the part of above-mentioned incident light to the direction reflection of above-mentioned ink gun, makes from the part of the light of above-mentioned ink gun reflection.
In droplet configuration device of the present invention, be preferably, above-mentioned ink gun by the nozzle bore of the liquid that spues, for liquid from said nozzle spue and produce pressure the balancing gate pit, to above-mentioned balancing gate pit supply with aforesaid liquid stream, store the container of aforesaid liquid and be used for aforesaid liquid is constituted from the pipe that said vesse is transported to above-mentioned stream; In above-mentioned ink gun, the surface that aforesaid liquid contacted is made of catoptrical material, and has light source is incided structure in the said vesse.
Of the present invention with the method for droplet configuration on substrate, be to spue liquid and aforesaid liquid is configured in the lip-deep method of aforesaid substrate from ink gun, photo detector is configured in the liquid exhaust end of above-mentioned ink gun, again aforesaid substrate is configured between above-mentioned ink gun and the above-mentioned photo detector, before the aforesaid liquid that spues, measure the position of above-mentioned ink gun by above-mentioned photo detector, determine the relative position of above-mentioned ink gun and aforesaid substrate aforesaid liquid to be configured on the aforesaid substrate according to above-mentioned measured information.
If adopt drop mobile device of the present invention, then can correctly make electronic installation and highdensity DNA chip.And then, because the computing circuit of relative position that is used for deriving optical system or ink gun and substrate is so long as simply just enough, so miniaturization and low price that can implement device.
(embodiment 1)
Fig. 1 is the schematic diagram of an example of expression droplet configuration device of the present invention.Drop 2 spues as arrow 3 to substrate 13 from ink gun 1, drop 2 is configured on the assigned position of fixing base 13.Ink gun 1 is fixed on the balladeur train 4, and balladeur train 4 moves along X-direction along balladeur train axle 5.Spue control circuit 9 control from spue size, initial velocity, the quantity of per drop that spued in 1 second 2 of the moment, drop 2 of drop 2 of ink gun 1.Substrate 13 be configured in photo detector 6 directly over, substrate 13 moves in the effect lower edge of the travelling carriage 7 that moves along balladeur train axle 8 Y direction integratedly with photo detector 6.Substrate 13 is preferably the material with light transmission.Balladeur train axle 8 moves while controlled by position control circuit 10 respectively with travelling carriage 7.The information that incides light intensity in the photo detector 6 and incoming position is by 11 inputs of photo detector signal processing circuit.
As the illustrated Fig. 2 in back, incide mechanism the photo detector owing to have, so utilize the position relation of the position relation of this light ink gun shown in Figure 1 as can be known 1 and photo detector 6 and substrate 13 and photo detector 6 from the light of the nozzle bore of the drop that spues and periphery radiation thereof.And then, according to these two information position relation of ink gun and substrate as can be known.In the present embodiment, owing to have from nozzle bore and peripheral mechanism thereof to the photo detector radiating light, so the bigger gap that is used for putting into light source need be set between photo detector 6 and substrate 13, can reduce the interval of substrate 13 and photo detector 6, no longer need large-scale optical system.Therefore, can make substrate 13 and photo detector 6 integrated motions.As a result, even ink gun 1 moves simultaneously with substrate 13, also can utilize the simple calculations circuit to derive the two relative position relation.
So-called in the present invention photo detector 6 is meant that the optical sensor that will experience light is arranged in the parts that form on the two dimensional surface, measures the light intensity that incides in each sensor.As representational photo detector, charge coupled cell (CCD) type imaging apparatus and metal-oxide semiconductor (MOS) (MOS) type imaging apparatus are arranged.
Fig. 2 is the schematic diagram that only part of the substrate 13 of the droplet configuration device of Fig. 1 and photo detector 6 is described in detail.Each optical sensor 16 is kept by optical sensor support portion 17, arranges planar with clathrate.If light incides in each optical sensor 16, then transform light energy is that electronic energy produces electric current in optical sensor 16.The electric current that in each element, produces be input in the photo detector signal processing circuit 18 amplify, calculation process.Photo detector signal processing circuit 18 will be experienced the position of optical sensor 16 of light and the information of intensity is carried out outside output as the signal of telecommunication.Carry out calculation process by the signal of telecommunication, can access the information that incides the light in the optical sensor 16 (photo detector) with 19 pairs of these outputs of computer.If with object lens 20 be configured in optical sensor 16 top, adjust both distance, make optical sensor 16 tops the centrally aligned of picture of ink gun to optical sensor, then can derive the position relation of ink gun and each optical sensor 16.If be predetermined the position of substrate 14 and optical sensor 16 (photo detector), also determine the nozzle bore of ink gun and the position of optical sensor 16 (photo detector) to concern, also just known the position relation of nozzle bore and substrate, so the disgusting as can be known position that goes out the substrate of drop.The whole photo detector of 15 expressions.
Even without the position that determines substrate and photo detector in advance closely,, also can detect the position relation of ink gun and substrate if adopt following method.That is, on the optical sensor and after deriving the position relation of nozzle bore and imaging apparatus, the centrally aligned of picture that makes substrate equally is on imaging apparatus and the position of deriving substrate and imaging apparatus concerns at the centrally aligned of the nozzle bore picture that makes ink gun.According to these two information, can derive the position relation of nozzle bore and substrate.
(embodiment 2)
Fig. 3 A is the schematic diagram of an example of expression present embodiment.Under transparency carrier 23, be provided with the optical unit 27 that inside has reflecting plate 28.28 pairs of light of reflecting plate are translucent, and the incident light 24 that enters abreast with the face of substrate 23 is become the reverberation 25 to ink gun 21 by reflecting plate 28 reflections.This reverberation 25 is reflected by nozzle plate 33 and substrate 23 and becomes reverberation 26, is formed the picture of nozzle plate 33 and substrate 23 by optical sensor 31 by reflecting plate 28, by object lens 30.32 expression optical sensor support portions, the whole photo detector of 29 expressions.
Fig. 3 B is the upward view of the ink gun 21 of Fig. 3 A, and expression has the nozzle plate 33 of a plurality of nozzle bores 22.
(embodiment 3)
Fig. 4 has been to use the schematic diagram of an example of the droplet configuration device of the ink gun shown in the present embodiment.From the nozzle bore of ink gun 34 to transparent substrate 36 irradiates lights 35.The light 35 that is shone enters into optical sensor 39 by object lens 38, so can derive the position relation of nozzle bore and photo detector.In addition, if this illumination is mapped on the substrate 36, then also can passes through optical sensor (photo detector) 39 and derive the positional information of substrate 36.40 expression optical sensor support portions, the whole photo detector of 37 expressions.
Fig. 5 emits light 42 and detects another example of the position of ink gun 41 and substrate 43 from the nozzle of ink gun 41.Basically identical with Fig. 4, but feature in this example is not have object lens.By making optical sensor 45 approaching, also can detect the position of nozzle bore even without object lens with the distance of ink gun 41.46 expression optical sensor support portions, the whole photo detector of 44 expressions.
Fig. 6 is a schematic diagram of representing the structure of the ink gun 51 that uses in the present embodiment particularly.The inwall of the inwall of the inwall of the nozzle bore of offering on nozzle plate 54 55, the inwall of balancing gate pit 56, black stream 57, pipe 59 and the inwall of liquid container 61 are formed by catoptrical material.In order to make each inwall become such material, can be on each inwall evaporation or the higher metal of plating light reflectivity.Employed metal has aluminium, platinum, gold etc.If light source 62 is arranged in the liquid container 61 and radiating light, the then inwall of the light 60 managed 59 that penetrates from light source, the inwall of black stream 57, the inwall of balancing gate pit 56, the inwall reflection of nozzle bore 55 finally becomes from what nozzle bore 55 was outwards emitted and emits light 63.Light source 62 might not be arranged in the liquid container 61, for example also can be arranged on the outside of container, directs light in the container by optical fiber.The 52nd, piezoelectric element, the 53rd, oscillating plate, the 58th, supply port.
Fig. 7 is the figure that schematically represents from the shape of the light beam of nozzle bore 64 radiation.Being shaped as of the nozzle bore 64 that runs through nozzle plate 63, from the light beam 65 of nozzle bore 64 radiation central shaft symmetry with respect to nozzle bore 64 with respect to central shaft when symmetry of passing nozzle bore 64 centers.Thereby, if this light beam 65 is projected on the set dignity of optical sensor 67, then become circular hot spot 66.Since consistent directly over the central point of this circular hot spot 66 with the central part of nozzle bore 64, so can detect the center of nozzle bore 64.
Specific embodiment of the present invention below is described.In addition, the present invention is not limited to following
Embodiment.
(embodiment 1)
Using the droplet configuration device, is on the glass substrate of long 10mm, wide 10mm, thickness 0.2mm in size, has disposed liquid with the interval of 100 μ m in the round inner region of diameter 50 μ m.Below represent its details.
(1) manufacture method of substrate
Be that the tabular quartz glass substrate of long 10mm, wide 10mm, thickness 0.2mm cleans the back with the neutral detergent ultrasonic wave and cleans with pure water with size.Blow this glass substrate and after the drying with nitrogen, irradiation ultraviolet radiation in 110 ℃ ozone environment gas and the organic matter that will remain on the glass baseplate surface are removed.Then, utilize common photoetching process, on four angles of glass substrate, form the location mask (alignment mask) of chromium.Alignment mask forms 2 long 100 μ m, wide by 10
The cross shape that the rectangle of μ m meets at right angles and intersects.Then, on this glass substrate, form the figure of eurymeric resist film.This figure is that the resist film by the circle of diameter 50 μ m is that clathrate forms with being spaced of 100 μ m.Close the position that makes the alignment mask on four jiaos that are formed on the glass substrate and justify is the value that is predetermined.That is,, just can know the position of the circle of regulation definitely if know the position of four jiaos alignment mask.
Then, in being full of the spherical case of drying nitrogen, glass substrate is immersed in the mixed solution (volume ratio 8: 2) of the n-hexadecane of the ten hexafluoro ethyl trichlorosilanes that dissolved 1vol% (below be called " FACS ") and chloroform 1 hour.Then, clean this glass substrate with toluene.As a result, FACS is adsorbed on the zone that does not have resist.
Then, from spherical case, take out the glass substrate after handling, be immersed in the acetone, the resist film on the glass substrate is removed.Owing to the FACS that is adsorbed on the glass substrate can not removed, be hydrophily so only removed the zone of resist by the acetone dipping.As a result, be the circle of diameter 50 μ m with the hydrophilic zone of the arranged spaced of 100 μ m, be hydrophobicity beyond this hydrophilic region, can form the figure of hydrophilic/hydrophobic.In addition, the static contact angle with respect to pure water of water repellent region and hydrophilic region is respectively 5 degree and 130 degree.
(2) optical sensor
As optical sensor, use the charge coupled cell (CCD) of the electric industry corporate system of Panasonic.Specification is as follows.
Number of sensors: 30,000
An optical sensor and periphery is shared is of a size of: long 60 μ m, wide 60 μ m
All the sensors is shared to be of a size of: long 15mm, wide 15mm
(3) ink gun
Use the general ink gun shown in Figure 11 A～Figure 11 B.Oscillating plate is the copper of thickness 3 μ m, and piezoelectric element is the lead zirconate titanate (PZT) of thickness 3 μ m.PZT forms with the vacuum splashing and plating method, (001) orientation on the vertical direction of film.Nozzle plate has been implemented hydrophobic treatment.The diameter of nozzle bore is 20 μ m, forms by the discharge processing method.In addition, shown in Figure 11 C, the nozzle number of the China ink of the same color that spues is 40, it with about being spaced of 340 μ m.And the arranged spaced 5 with 170 μ m under the listing of 40 nozzles is listed as.The Volume Composition of nozzle bore is 200.In the present embodiment, only use a nozzle bore to carry out spuing of liquid.Spuing of liquid is to be undertaken by the frequency that applies 10KHz between piezoelectric element, the voltage of amplitude 20V.The drop amount is 20 skin liters (the about 16.8 μ m of radius).The liquid of the regulation of having packed in ink gun replaces China ink.
(4) droplet configuration device
Fig. 8 is the concept map of the droplet configuration device of present embodiment, and is except having added light reflector element 73 and light source 83, identical with droplet configuration device shown in Figure 1.Be disposed with photo detector 74, light reflector element 73, glass substrate 72 on travelling carriage 75, travelling carriage 75 moves on Y direction along balladeur train axle 76.Ink gun 71 moves in balladeur train axle 78 upper edge X-directions with balladeur train 77.The distance of the nozzle plate of ink gun 71 and glass substrate 72 is set at 0.3mm.In addition, will import to the light reflector element 73 from light source 83 with parallel incident light 84 in the face of glass substrate 72.In the present embodiment, in light source, use Halogen lamp LED.The 79th, photo detector signal processing circuit, the 80th, position control circuit, the 81st, the control circuit that spues, the 82nd, computer.
Fig. 9 is the schematic diagram that explains the structure of photo detector and light reflector element.Light reflector element 91 is provided with catoptrical reflecting part 92.92 pairs of light of this reflecting plate are translucent, the part of incident light 93 that will be parallel with the face of glass substrate reflection and become reverberation 94, the transmission of a part of light former state.The glass substrate (diagram omit) of reverberation 94 by being arranged on top arrives the nozzle plate (diagram is omitted) of ink gun (diagram is omitted), becomes reverberation and gets back to reflecting plate once more.The part of this light incides in the photo detector 97.Photo detector 97 is that CCD and the object lens that are located at its top 95 constitute by the aggregate of optical sensor 96.The distance of object lens 95 and CCD is controlled by electromagnetic motor.
(5) be configured in liquid on the glass substrate
(the strand oligonucleotide (with the pure medicine system of light) that is made of 10 bases of fluorescein isothiocyanate (FITC) fluorescence labelling is dissolved in the pure water with 20wt% with fluorescein isothiocynate with end.Be inserted in the black chamber of ink gun.
(6) to the method for glass substrate configuration liquid
Utilize the collocation method of Fig. 8 express liquid.After inciding light reflector element 73 from light source 83 incident light 84, adjust the distance of object lens (Fig. 9 95) and CCD, so that the center of the picture of glass substrate 72 lip-deep alignment mask is on CCD element 74.As a result, can derive the position relation of alignment mask and CCD element.Equally, mobile object lens are derived the position relation of nozzle bore and CCD element so that the center of the picture of the nozzle bore of the liquid that spues on the nozzle plate is just being dropped on the CCD element.Measure by these, the position that can derive each hydrophilic region and nozzle bore on the glass substrate 72 concerns.Then, the position of mobile ink gun 71 and glass substrate 72 so that the nozzle bore of the liquid that spues want to dispose hydrophilic region on the glass substrate 72 of liquid directly over.Then, by control circuit 81 from ink gun 71 drop that spues.Equally, mobile ink gun 71 is configured in liquid on the next hydrophilic region.Repeat these actions, liquid is configured on all hydrophilic regions on the glass substrate 72.
With the situation of droplet configuration on substrate, can utilize photo detector, photo detector signal processing circuit 79, computer 82 from ink gun 71, observe at the scene.That is, consistent by the picture that makes center (focus) and nozzle bore, can observe from the spue situation of liquid of nozzle bore.As a result, as can be known can field observation spuing, not spuing from the liquid of nozzle bore.
(7) evaluation method of the liquid that is disposed and result
The oligonucleotide that is configured on the glass substrate is identified by fluorescent material, so by can estimate the shape of the drop that is disposed with light microscopic examination fluorescence.The laser of wavelength 400nm is radiated on the glass substrate, observes the fluorescence of 520nm.
The result can confirm, sends fluorescence from the round inner region of diameter 50 μ m, and this zone is with the arranged spaced of 100 μ m.
(embodiment 2)
Dispose drop similarly to Example 1.Wherein, ink gun is as follows.
(1) ink gun
Utilize the ink gun of the structure shown in Figure 6 of embodiment 3.Use Halogen lamp LED as light source.In addition, the inwall of the head inwall of aluminium that adopted vacuum evaporation.
(2) to the method for glass substrate configuration liquid
Adjust object lens and imaging apparatus at interval, make the center of nozzle bore of radiating light consistent with the CCD component side, the position of derivation nozzle bore and imaging apparatus concerns.Then, ink gun, substrate, imaging apparatus are moved so that from the illumination of nozzle bore radiation on the alignment mask on the substrate.In addition, substrate and imaging apparatus move integratedly.Then, make the center of picture of alignment mask of substrate consistent with the CCD element, the position of deriving alignment mask and imaging apparatus concerns.Based on these 2 position relations, derive the position relation of nozzle bore and substrate.Then, according to this information, in the hydrophilic region of droplet configuration on substrate.
(3) evaluation method of the liquid that is disposed and result
With being configured in drop on the glass substrate with the same method evaluation of embodiment.The result can confirm, and is the same with embodiment 1, sends fluorescence from the round inner region of diameter 50 μ m, and this zone is with the arranged spaced of 100 μ m.
(embodiment 3)
Similarly to Example 2 with droplet configuration on glass substrate.Wherein, object lens are got from imaging apparatus removed.And, the CCD element is contacted with glass substrate.
Similarly to Example 2, derive the relative position of nozzle bore and substrate, with droplet configuration on the position of stipulating.As a result, similarly to Example 2, can confirm that drop correctly is configured on the position of regulation.
Industrial applicibility
The present invention is owing to being configured in small drop on the substrate accurately, so can Form small drop figure at substrate accurately. Be DNA by making the drop that spues Probe, protein, semi-conducting material, lens material, metal material can form the DNA core Semiconductor element, lens, the wirings such as sheet, biochip, thin film transistor (TFT). Thereby, by The present invention can realize DNA chip, biochip and electronic component etc.
In addition, use in an embodiment of the present invention piezoelectric element to produce as the pressure of ink gun Mechanism, but do not need to be defined in this, also can utilize by heat effect to produce bubble in moment Method (bubble jet (registration mark) method).
And then, in an embodiment of the present invention, only from the nozzle bore drop that spues, but also can With the drop that spues simultaneously from a plurality of nozzle bores.
Claims (14)
1, a kind of droplet configuration device is characterized in that,
Have: ink gun; Substrate is accepted the drop that spues from above-mentioned ink gun; Shine or catoptrical device to aforesaid substrate from nozzle bore or its periphery of above-mentioned ink gun; Location mobile device is controlled the relative position of above-mentioned ink gun and aforesaid substrate; Control device will spue from the liquid of above-mentioned ink gun;
The photo detector of discerning the position of above-mentioned ink gun is configured in from the rear of the aforesaid substrate of above-mentioned ink gun observation;
Aforesaid substrate has to be made from the said nozzle hole or the transparency of the degree that its periphery enters into photo detector to the irradiates light or the reverberation of aforesaid substrate;
Above-mentioned photo detector detect from the said nozzle hole or its periphery to the irradiates light or the reverberation of aforesaid substrate.
2, droplet configuration device as claimed in claim 1 is characterized in that, also has the mechanism that above-mentioned photo detector is also moved with the aforesaid substrate one.
3, droplet configuration device as claimed in claim 1 is characterized in that,
Between aforesaid substrate and above-mentioned photo detector, place the translucent reflecting plate of light;
Setting makes the light parallel with the face of aforesaid substrate incide light source on the said reflection plate;
Adjust the configuration said reflection plate, be transmitted to above-mentioned photo detector side so that the part of above-mentioned incident light to the direction reflection of above-mentioned ink gun, makes from the part of the light of above-mentioned ink gun reflection.
4, droplet configuration device as claimed in claim 1 is characterized in that, above-mentioned ink gun has in the nozzle bore of the liquid that spues the mechanism to the aforesaid substrate irradiates light.
5, droplet configuration device as claimed in claim 4 is characterized in that,
In the said nozzle hole to the mechanism of aforesaid substrate irradiates light have the said nozzle hole, for aforesaid liquid from nozzle spue and produce pressure the balancing gate pit, to above-mentioned balancing gate pit supply with aforesaid liquid stream, store the container of aforesaid liquid and be used for aforesaid liquid is transported to from said vesse the pipe of above-mentioned stream;
The surface of aforesaid liquid contact is made of catoptrical material, and incides light source in the said vesse and be directed to the said nozzle hole.
6, droplet configuration device as claimed in claim 1 is characterized in that, aforesaid substrate is glass or resin.
7, droplet configuration device as claimed in claim 1 is characterized in that, above-mentioned ink gun be by the vibration of using piezoelectric element spue liquid head or produce the head of the liquid that spues by the bubble that heat effect brings.
8, a kind of droplet configuration method spues liquid and aforesaid liquid is configured on the aforesaid substrate surface from ink gun, it is characterized in that,
Photo detector is configured in the liquid exhaust end of above-mentioned ink gun, again aforesaid substrate is configured between above-mentioned ink gun and the above-mentioned photo detector, before the aforesaid liquid that spues, measure the position of above-mentioned ink gun by above-mentioned photo detector, determine the relative position of above-mentioned ink gun and aforesaid substrate aforesaid liquid to be configured on the aforesaid substrate according to above-mentioned measured information.
9, droplet configuration method as claimed in claim 8 is characterized in that, also has the mechanism that above-mentioned photo detector is also moved with the aforesaid substrate one.
10, droplet configuration method as claimed in claim 8 is characterized in that,
Between aforesaid substrate and above-mentioned photo detector, place the translucent reflecting plate of light;
Setting makes the light parallel with the face of aforesaid substrate incide light source on the said reflection plate;
Adjust the configuration said reflection plate, be transmitted to above-mentioned photo detector side so that the part of above-mentioned incident light to the direction reflection of above-mentioned ink gun, makes from the part of the light of above-mentioned ink gun reflection.
11, droplet configuration method as claimed in claim 8 is characterized in that, above-mentioned ink gun has in the nozzle bore of the liquid that spues the mechanism to the aforesaid substrate irradiates light.
12, droplet configuration method as claimed in claim 11 is characterized in that,
In the said nozzle hole to the mechanism of aforesaid substrate irradiates light have the said nozzle hole, for aforesaid liquid from nozzle spue and produce pressure the balancing gate pit, to above-mentioned balancing gate pit supply with aforesaid liquid stream, store the container of aforesaid liquid and be used for aforesaid liquid is transported to from said vesse the pipe of above-mentioned stream;
The surface of aforesaid liquid contact is made of catoptrical material, and incides light source in the said vesse and be directed to the said nozzle hole.
13, droplet configuration method as claimed in claim 8 is characterized in that, aforesaid substrate is glass or resin.
14, droplet configuration method as claimed in claim 8 is characterized in that, above-mentioned ink gun be by the vibration of using piezoelectric element spue liquid head or produce the head of the liquid that spues by the bubble that heat effect brings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004077003 | 2004-03-17 | ||
| JP077003/2004 | 2004-03-17 |
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| CN1839045A true CN1839045A (en) | 2006-09-27 |
| CN100488777C CN100488777C (en) | 2009-05-20 |
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| CNB2005800007599A Expired - Fee Related CN100488777C (en) | 2004-03-17 | 2005-03-02 | Liquid drop placing device and liquid drop placing method |
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| Country | Link |
|---|---|
| US (1) | US7628464B2 (en) |
| JP (1) | JP4642756B2 (en) |
| CN (1) | CN100488777C (en) |
| WO (1) | WO2005090081A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927600A (en) * | 2009-06-22 | 2010-12-29 | 株式会社爱发科 | Blowoff and jet method |
| CN103649622A (en) * | 2011-07-05 | 2014-03-19 | 住友化学株式会社 | Method for manufacturing optical sheet |
| CN106965554A (en) * | 2012-01-02 | 2017-07-21 | 穆特拉茨国际有限公司 | Pickup and printing |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100488777C (en) * | 2004-03-17 | 2009-05-20 | 松下电器产业株式会社 | Liquid drop placing device and liquid drop placing method |
| JP4916697B2 (en) * | 2005-10-18 | 2012-04-18 | 株式会社アルバック | Ink coating apparatus, ejection nozzle inspection method, and ink coating method |
| JP5313022B2 (en) * | 2009-04-09 | 2013-10-09 | 株式会社ディスコ | Workpiece cutting method |
| KR101681189B1 (en) * | 2015-01-30 | 2016-12-02 | 세메스 주식회사 | Inspecting unit and method, Apparatus for treating a substrate with the unit |
| KR102026891B1 (en) * | 2017-02-06 | 2019-09-30 | 에이피시스템 주식회사 | Dispensing apparatus |
| TW202323068A (en) * | 2018-12-05 | 2023-06-16 | 美商凱特伊夫公司 | Substrate holder assembly and inkjet printer with substrate height position control |
| US11123983B2 (en) * | 2018-12-20 | 2021-09-21 | Kateeva, Inc. | Inkjet printer with substrate flatness detection |
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| JP3325931B2 (en) * | 1992-11-04 | 2002-09-17 | コニカ株式会社 | Marking method for photosensitive material |
| JP3241341B2 (en) | 1994-12-16 | 2001-12-25 | キヤノン株式会社 | Manufacturing method of electron source substrate |
| JP3241251B2 (en) * | 1994-12-16 | 2001-12-25 | キヤノン株式会社 | Method of manufacturing electron-emitting device and method of manufacturing electron source substrate |
| US5658802A (en) | 1995-09-07 | 1997-08-19 | Microfab Technologies, Inc. | Method and apparatus for making miniaturized diagnostic arrays |
| US6494563B2 (en) * | 1997-12-25 | 2002-12-17 | Canon Kabushiki Kaisha | Ink jet element substrate and ink jet head that employs the substrate, and ink jet apparatus on which the head is mounted |
| JP2001284047A (en) | 2000-04-03 | 2001-10-12 | Sharp Corp | Manufacturing method of an organic electroluminescence display device |
| JP2002253200A (en) | 2001-02-28 | 2002-09-10 | Canon Inc | Probe solution delivery device and method for identifying delivery state |
| JP2002286732A (en) | 2001-03-28 | 2002-10-03 | Canon Inc | Liquid discharge device used in manufacturing probe carrier, method of manufacturing probe carrier, and device of manufacturing probe carrier |
| JP2003098172A (en) | 2001-09-27 | 2003-04-03 | Matsushita Ecology Systems Co Ltd | Sensor device manufacturing method and apparatus, spotting apparatus, and needle tube body for spotting apparatus |
| US6952536B2 (en) * | 2003-10-04 | 2005-10-04 | Hewlett-Packard Development Company, L.P. | Transmissive optical sensing of leading edges of media sheets advanced substantially adjacent to one another |
| CN100488777C (en) * | 2004-03-17 | 2009-05-20 | 松下电器产业株式会社 | Liquid drop placing device and liquid drop placing method |
-
2005
- 2005-03-02 CN CNB2005800007599A patent/CN100488777C/en not_active Expired - Fee Related
- 2005-03-02 JP JP2006519386A patent/JP4642756B2/en not_active Expired - Fee Related
- 2005-03-02 WO PCT/JP2005/003514 patent/WO2005090081A1/en active Application Filing
- 2005-03-02 US US10/568,059 patent/US7628464B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927600A (en) * | 2009-06-22 | 2010-12-29 | 株式会社爱发科 | Blowoff and jet method |
| CN101927600B (en) * | 2009-06-22 | 2013-11-27 | 株式会社爱发科 | Discharge apparatus and discharge method |
| CN103649622A (en) * | 2011-07-05 | 2014-03-19 | 住友化学株式会社 | Method for manufacturing optical sheet |
| CN106965554A (en) * | 2012-01-02 | 2017-07-21 | 穆特拉茨国际有限公司 | Pickup and printing |
| CN106965554B (en) * | 2012-01-02 | 2018-12-21 | 穆特拉茨国际有限公司 | Ink-jet system |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080158300A1 (en) | 2008-07-03 |
| JPWO2005090081A1 (en) | 2008-01-31 |
| US7628464B2 (en) | 2009-12-08 |
| CN100488777C (en) | 2009-05-20 |
| JP4642756B2 (en) | 2011-03-02 |
| WO2005090081A1 (en) | 2005-09-29 |
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